EP0416659A2 - Procédé de préparation de particules de polymères - Google Patents

Procédé de préparation de particules de polymères Download PDF

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Publication number
EP0416659A2
EP0416659A2 EP90117311A EP90117311A EP0416659A2 EP 0416659 A2 EP0416659 A2 EP 0416659A2 EP 90117311 A EP90117311 A EP 90117311A EP 90117311 A EP90117311 A EP 90117311A EP 0416659 A2 EP0416659 A2 EP 0416659A2
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EP
European Patent Office
Prior art keywords
isocyanate compound
surfactant
per molecule
groups per
particles
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Application number
EP90117311A
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German (de)
English (en)
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EP0416659B1 (fr
EP0416659A3 (en
Inventor
Hironori Kataoka
Kazuhito Jinno
Tokiko Yamashita
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DKS Co Ltd
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Dai Ichi Kogyo Seiyaku Co Ltd
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Priority claimed from JP1234476A external-priority patent/JP2613480B2/ja
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Publication of EP0416659A3 publication Critical patent/EP0416659A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0833—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups together with anionic or anionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units

Definitions

  • the present invention relates to a method of producing a particulate polymer.
  • Particulate polymers are intended for use as matting agents for paints, additives to suede- or velvet-texture coatings, cosmetic products, agro­chemicals, drugs, etc. and it is foreseen that these polymers will find application in a still greater variety of fields in the years to come.
  • par­ticulate polymers are the method which comprises reacting a polyester or polyether with an isocyanate in the presence of an oil-modified alkyd resin in a solvent (Japanese Patent Publication No. 50-8116) and the method which comprises the steps of emulsifying a mixture of a polyol and a polyisocyanate in the presence of an emulsifier and a protective colloid in water and, then, adding a polyamine or a catalyst (Japanese Patent Publication No. 51-34880, No. 51-10878 and No. 56-9531).
  • an oil-­soluble or water-soluble protective colloid such as oil-modified alkyd resin, polyvinyl alcohol, gelatin or the like, in order to preclude aggregation of particles during the curing reaction.
  • the object of the present invention is to overcome the above-mentioned disadvantages of the prior art manufacturing technologies and provide a method of producing a particulate polymer which dispenses with a protective colloid and yet is free from the aggregation of particles during and after the curing reaction.
  • the method of producing a particulate polymer according to the present invention is characterized in that a mixture of an isocyanate compound having two or more isocyanato groups per molecule and a surfactant having two or more hydroxyl groups per molecule is emulsified and dispersed in a dispersing medium which does not dissolve said isocyanate compound without addition of a protective colloid and cured as it is.
  • the isocyanate compound having two or more isocyanato groups per molecule include various polyisocyanates and urethane prepolymers.
  • the polyisocyanates mentioned above include, inter alia , tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, tolidine diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethane triisocyanate, hexamethylene triisocyanate, polymethyl­ene polyphenyl isocyanate, tolylene diisocyanate trimer and so on.
  • the urethane prepolymers mentioned above include, inter alia , the isocyanato-terminated isocyanates obtainable by reacting the known polyols with excesses of said polyisocyanate compounds.
  • the known polyols include polyhydric alcohols, polyether polyols, polycarbonate polyols, acrylic polyols, polyester polyols, silicone polyols and so on.
  • any one of the compounds mentioned above may be selectively used or, if desired, more than one of them can be selectively used.
  • these isocyanate compounds a broad spectrum of particulate polymers ranging from very hard particles to soft and flexible particles can be manufactured. Generally, hard parti­cles are obtained when a polyol-free polyisocyanate compound or a urethane prepolymer containing a short-­chain polyol component is employed, while flexible particles are obtained when a urethane prepolymer containing a long-chain polyol component is employed.
  • an aliphatic polyisocyanate yields particles which are hard to undergo yellowing and resistant to weather.
  • any of nonionic surfac­tants, anionic surfactants, cationic surfactants and amphoteric surfactants can be employed.
  • the nonionic surfactants containing two or more hydroxyl groups per molecule include, inter alia , polyoxyethylene-polyoxypropylene block polymer, sorbitol fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, fatty acid monoglycerides, polyoxyalkylene fatty acid monoglycerides, polyglycerin fatty acid esters, polyoxyalkylene castor oil ethers, polyoxyalkyl­ene alkylamines, polyoxyalkylene alkylamides and so on.
  • the anionic surfactants containing two or more hydroxyl groups per molecule include, inter alia , castor oil monosulfate, castor oil monophosphate, sorbitan fatty acid ester sulfate, sorbitan fatty acid ester phosphate, sorbitol fatty acid ester sulfate, sorbitol fatty acid ester phosphate, sucrose fatty acid ester sulfate, sucrose fatty acid ester phosphate, polyoxyalkylene castor oil ether monosulfate, poly­oxyalkylene castor oil ether monophosphate, polyoxyalky­lene sorbitan fatty acid ester sulfate, polyoxyalkylene sorbitan fatty acid ester phosphate, polyoxyalkylene glycerin ether monosulfate, polyoxyalkylene glycerin ether monophosphate and so on.
  • the cationic surfactants containing two or more hydroxyl groups per molecule include, inter alia , dialkanolamine salts, trialkanolamine salts, polyoxy­alkylene alkylamine ether salts, trialkanolamine fatty acid ester salts, polyoxyalkylene dialkanolamine ether salts, polyoxyalkylene trialkanolamine ether salts, di(polyoxyalkylene)alkylbenzylalkylammonium salts, alkylcarbamoylmethyldi(polyoxyalkylene)ammonium salts, polyoxyalkylenealkylammonium salts, polyoxyalkylene­ dialkylammonium salts and so on.
  • amphoteric surfactants containing two or more hydroxyl groups per molecule include, inter alia , N,N-di( ⁇ -hydroxyalkyl)-N-hydroxyethyl-N-carboxyalkylam­monium betaine, N- ⁇ -hydroxyalkyl-N,N-dipolyoxyalkylene-N-­carboxyalkylammonium betaine, N-alkyl-N,N-di(polyoxy­alkylene)amine dicarboxylic acid monoesters, N-(polyoxy­ethylene-N′,N′-di(polyoxyethylene)aminoalkyl-N-alkyl-N-­sulfoalkylammonium betaine, N,N-di(polyoxyethylene)-N-­alkyl-N-sulfoalkyleneammonium betaine, N-( ⁇ -hydroxyalkyl­aminoethyl)-N-( ⁇ -hydroxyalkyl)aminoethy
  • surfactants may be used either independently or in combination.
  • the diameter of the product particles can be controlled. Assuming that the same kind of surfactant is employed, the use of it in a larger proportion results in a smaller particle dia­meter and the reverse is true, too.
  • the propor­tion is dependent on the desired particle diameter but is generally not less than 3 percent by weight based on the isocyanate compound.
  • the surfactant containing two or more hydroxyl groups per molecule acts not only as an emulsifier-dis­persing agent but also reacts with the isocyanate compound to act as a curing agent for the polymer, it is preferably used in an excess over the usual amount for emulsification.
  • a known emulsifier-dispersing agent may be previously incorporated in the dispersing medium to assist in the emulsification of the mixture of said isocyanate compound and said surfactant containing two or more hydroxyl groups per molecule.
  • the dispersing medium to be employed in the present invention may be virtually any medium that does not dissolve but disperse said isocyanate compound, but water or an organic solvent inert to isocyanato groups is preferred.
  • organic solvents which do not dissolve but disperse the isocyanate compound and is inert to isocyanato groups there can be mentioned organic solvents which do not contain any active hydrogen-containing functional groups, which are reactive to isocyanato groups, such as -OH, -NH2, -SH and so on.
  • organic solvent can be selected from among paraffin, esters, ketones, aromatic hydrocarbons, halogen compounds, ethers, and so on. These solvents may be used in combination.
  • the proportion of the surfactant containing two or more hydroxyl groups per molecule is 3 to 95 percent by weight and preferably 5 to 60 percent by weight based on the isocyanate compound.
  • the proportion of said surfactant is 3 to 1000 percent by weight based on the isocyanate compound.
  • the surfactant is entrapped in the particul­ ate polymer by way of urethane linkages, the particles are not agglomerated but can be dispersed so efficient­ly that a protective colloid is not required.
  • a catalyst of the conventional amine type or metal type can be added.
  • a known polyamine compound can be added.
  • Such catalyst and crosslinking agent may be added to the dispersing medium or a mixture of said isocyanate compound and said surfactant.
  • Sufficient emulsification can be achieved by the usual stirring technique (50 to 1000 rpm) in many cases but a homodisperser, homogenizer or the like can be employed as necessary.
  • the weight ratio of the mixture to be emulsified to the dispersing medium is generally about 1:0.5 to 1:100 and preferally about 1:1 to 1:20.
  • the curing reaction time varies with the kind of isocyanate compound, the type and amount of catalyst, the reaction temperature, etc., it is general­ly about 5 minutes to one day.
  • the curing reaction temperature is generally 5 to 100°C and preferably room temperature to 80°C.
  • the curing reaction results in the formation of a slurry which may be used as it is or as processed into a powder by filtration and drying.
  • the filtration and drying processes are not critical and may be conducted under the conventional conditions.
  • Colored particles can be produced by incorporating a colorant in a mixture of said isocyanate compound and said surfactant containing two or more hydroxyl groups per molecule.
  • a coating film having a suede-like or velvet-like texture is obtained.
  • the colorant used for this purpose the known organic pigments, inorganic pigments and dyes can be used.
  • the addition level of such a colorant is about 0.1 to 90 percent by weight relative to the isocyanate compound.
  • a sufficient mixing effect can be generally achieved by the usual stirring technique (50 ⁇ 1000 rpm) because of the comparatively large amount of surfactant contained but, if necessary, a kneader, ball-mill, bead-mill, roller mill, homodisperser, homogenizer or the like may be employed for mixing.
  • a diluent solvent is preferably added.
  • the diluent solvent should be chosen from among those not reactive to the dispersing agent.
  • parti­culate polymers having various functions can be pro­duced by incorporating various drugs or the like in mixtures of said isocyanate compound and said surfactant containing two or more hydroxyl groups.
  • the present invention accordingly offers the following effects.
  • a urethane prepolymer prepared by reacting 1 mole of trimethylolpropane with 3 moles of tolylene diisocyanate, was used as the isocyanate compound.
  • a polyoxyethylene-polyoxypropylene block polymer (mol. wt. 1,000, polyoxyethylene content 20 wt. %) was used as the nonionic surfactant contain­ing two or more hydroxyl groups per molecule.
  • a mixture of the above-mentioned urethane prepolymer (100 g) and nonionic surfactant (30 g) was added to 700 g of water under stirring with a magnetic stirrer and the curing reaction was carried out at 40°C with continued stirring (300 ⁇ 500 rpm) for 5 hours. The resulting slurry was suction-filtered and dried in the air to give nonionic beads with an average diameter of 120 ⁇ m.
  • Example 2 The procedure of Example 1 was repeated except that 30 g of castor oil monosulfate calcium salt (an anionic surfactant) was used as the surfactant contain­ing two or more hydroxyl groups per molecule. As a result, anionic beads with an average diameter of 140 ⁇ m were obtained.
  • Example 2 The procedure of Example 1 was repeated except that 30 g of lauryldiethanolamine hydrochloride (a cationic surfactant) was used as the surfactant con­taining two or more hydroxyl groups per molecule. As a result, cationic beads with an average diameter of 90 ⁇ m were obtained.
  • lauryldiethanolamine hydrochloride a cationic surfactant
  • Example 2 The procedure of Example 1 was repeated except that 30 g of N,N-di( ⁇ -hydroxylauryl)-N-hydroxyethyl-N-­carboxybutylammonium betaine (an amphoteric surfactant) was used as the surfactant containing two or more hydroxyl groups per molecule. As a result, amphoteric particles with an average particle diameter of 100 ⁇ m were obtained.
  • a carbodiimide-modified diphenylmethane diiso­cyanate 100 g (the isocyanate compound), a polyoxy­ethylene-polyoxypropylene block polymer (mol. wt. 1,500, polyoxyethylene content 40 wt. %) (20 g) (the nonionic surfactant containing two or more hydroxyl groups per molecule) and 10 g of titanium dioxide (the colorant) were mixed in a beaker.
  • This mixture was added to 500 g of water under stirring with a magnetic stirrer and the curing re­action was carried out at 45°C with continued stirring (300 ⁇ 500 rpm) for 10 hours.
  • the average diameter of the resulting nonionic white beads was measured with a Coulter counter.
  • the average particle diameter of this product was 35 ⁇ m.
  • Example 5 The procedure of Example 5 was repeated except that, in lieu of the surfactant containing two or more hydroxyl groups per molecule, polyoxyethylene-nonyl­phenylether sulfate sodium salt was used as the emulsi­fier.
  • the average particle diameter of the resulting colored (white) beads was 40 ⁇ m.
  • the slurry was reduced to powder as in Example 5 and 30 g of the powder was added to 50 g of a commercial one-package urethane coating, followed by gentle stirring (300 rpm). However, the powder could not be evenly dis­persed. The beads could be dispersed only after 60 minutes of intense stirring at 5,000 rpm with a homodisperser.
  • the above result was brought about because the surfactant containing two or more hydroxyl groups per molecule was not used and, hence, the dispersibility of the beads was poor.
  • the film formed from this coating composition betrayed projections attributable to aggregation of particles.
  • Example 5 The procedure of Example 5 was repeated except that 20 g of polyvinyl alcohol in water was used as the protective colloid.
  • the resulting white particles had an average particle diameter of 33 ⁇ m.
  • the product slurry was suction-filtered. However, owing to the thickening effect of the protective colloid, the filtration procedure required 70 minutes. When the filter cake was dried in the air, the residual polyvinyl alcohol formed a film interconnecting the particles so that caking occurred to prevent formation of a neat powder. When this filter cake was washed with 2 portions of water and dried, a neat powder could be obtained.
  • Example 5 Compared with Example 5, this Comparative Example required a superfluous washing step for removal of the residual polyvinyl alcohol.
  • the colored particles obtained after washing and drying were less dispersible, owing to the residual polyvinyl alcohol, though its amount was small, than the particles of Example 5 and the coating film also betrayed projections due to aggregation of the parti­cles.
  • An isocyanato-terminated prepolymer 250 g (the isocyanate compound) which was obtained by reacting polypropylene glycol (mol. wt. 2,000) with tolylene diisocyanate, sorbitan monostearate monophosphate ester (50 g) (the anionic surfactant containing two or more hydroxyl groups per molecule), and carbon black (15 g) (the colorant) were mixed together in a ball mill for 30 minutes.
  • This mixture (100 g) was emulsified in 300 g of water under stirring with a magnetic stirrer and, then, triethylamine (1.5 g) was added as the catalyst.
  • the curing reaction was conducted at room temperature with stirring (500 rpm) for 5 hours.
  • the resulting slurry was suction-filtered and freeze-dried.
  • the resulting powder had an average particle diameter of 65 ⁇ m.
  • the black anionic beads thus obtained had an elastic and kind feeling.
  • This product was a cationic powder having an average par­ticle diameter of 20 ⁇ m.
  • This product was not soluble in any of methanol, ethanol, hexanol, hexane, iso­octane, xylene, toluene, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylform­amide, ethylcellosolve, ethylcellosolve acetate, machine oil and soybean oil, and thus exhibited excel­lent resistance to chemicals.
  • An isocyanato-terminated prepolymer (1,500 g) (the isocyanate compound) obtainable by reacting a polyester polyol (average mol. wt. 3,500) with tolylene diisocyanate and sucrose trioleate (45 g) (the nonionic surfactant) were mixed together and the mixture was added for emulsification to 3 kg of water containing 3 wt. % of sodium dioctylsulfosuccinate as the auxiliary emulsifier at 25°C. Then, 12 g of hexamethylenediamine was added as the crosslinking agent and the curing reaction was carried out with constant stirring (500 rpm) at 25°C for 7 hours. The resulting slurry was centrifuged and the resulting cake was freeze-dried to give a powder. Having an average particle diameter of 300 ⁇ m, this product was a transparent, elastic non-­ionic powder in the bead form.
  • sucrose trioleate as the surfac­tant was used in varying amounts of 50 g, 100 g, 200 g and 500 g.
  • the average particle diameters of the respective products are shown in Table 1.
  • Table 1 The amount of sucrose trioleate (g) 50 100 200 500
  • Example 5 The procedure of Example 5 was repeated except that 10 g of O,O-diisopropyl-S-benzylthiophosphate (a fungicide) was used as the agrochemical in lieu of the colorant. As a result, fungicidal beads having an average particle diameter of 33 ⁇ m were obtained.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of pyrethrin (an insecticide) was used as the agrochemical in lieu of the colorant. As a result, insecticidal beads having an average particle diameter of 35 ⁇ m were obtained.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of aspirin (an antipyretic-analgesic) was used as the drug in lieu of the colorant. As a result, aspirin-containing beads having an average particle diameter of 37 ⁇ m were obtained.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of ⁇ -glucosidase of yeast origin was used as the enzyme in lieu of the colorant. As a result, ⁇ -glucosidase-containing beads having an average particle diameter of 33 ⁇ m were obtained.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of lemon oil was used as the perfume in lieu of the colorant. As a result, beads giving off a lemon-like fragrance was obtained. The average parti­cle diameter of this product were 35 ⁇ m.
  • Example 5 The procedure of Example 5 was repeated except that 2 g of muscone was used as the perfume in lieu of the colorant.
  • the resulting muscone-containing beads had an average particle diameter of 37 ⁇ m.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of essential oil was used as the deodorant in lieu of the colorant.
  • the resulting essential oil-con­taining beads had an average particle diameter of 32 ⁇ m.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of copper dust was used in lieu of the colorant.
  • the resulting copper dust-containing beads had an average particle diameter of 35 ⁇ m.
  • Example 5 The procedure of Example 5 was repeated except that 10 g of gold powder was used in lieu of the colorant. As a result, gold powder-containing beads having an average particle diameter of 34 ⁇ m were obtained.
  • a mixture of tolylene diisocyanate (174 g) (the isocyanate compound) and a polyoxyethylene-polyoxypro­pylene block polymer (mol. wt. 1,000, polyoxyethylene content 20 wt. %) (1,000 g) (the nonionic surfactant containing two or more hydroxyl groups per molecule) was added to 2,000 g of kerosene with stirring and the curing reaction was carried out with stirring (500 rpm) at 85°C for 2 hours.
  • the resulting slurry was suction-­filtered and dried in the air to give nonionic beads with an average particle diameter of 45 ⁇ m.
  • Example 19 The procedure of Example 19 was repeated except that 1,030 g of castor oil monosulfate ammonium salt (an anionic surfactant) was used as the surfactant containing two or more hydroxyl groups per molecule. As a result, anionic beads having an average particle diameter of 35 ⁇ m were obtained.
  • 1,030 g of castor oil monosulfate ammonium salt an anionic surfactant
  • Example 19 The procedure of Example 19 was repeated except that 240 g of lauryldiethanolamine hydrochloride (a cationic surfactant) was used as the surfactant con­taining two or more hydroxyl groups per molecule. As a result, cationic beads having an average particle diameter of 43 ⁇ m were obtained.
  • lauryldiethanolamine hydrochloride a cationic surfactant
  • Example 19 The procedure of Example 19 was repeated except that 305 g of N,N-di(hydroxyethyl)-N-lauryl-N-carboxy­methylammonium betaine (an amphoteric surfactant) was used as the surfactant containing two or more hydroxyl groups per molecule. As a result, amphoteric beads having an average particle diameter of 40 ⁇ m were obtained.
  • Hexamethylene diisocyanate (168 g) (the isocyanate compound), a polyoxyethylene-polyoxypropylene block polymer (mol. wt. 1,500, polyoxyethylene content 30 wt. %) (750 g) (the nonionic surfactant containing two or more hydroxyl groups per molecule) and titanium dioxide (140 g) (the colorant) were mixed together.
  • This mixture was added to 3,500 g of kerosene with stirring and, then, 58 g of hexamethylenediamine was added as the crosslinking agent.
  • the curing reaction was conducted under constant stirring (300-500 rpm) at 45°C for 10 hours.
  • the average diameter of the result­ ing nonionic white beads was 42 ⁇ m.
  • the slurry thus obtained was suction-filtered. The required filtration time was 10 minutes.
  • the filter cake was dried in vacuo at 60°C to give a neat powder.
  • This product 100 g was added to a commercial one-package urethane coating (140 g) and the mixture was gently stirred (300 rpm) to give a uniform disper­sion.
  • the coating film was elastic and white, with a suede-like texture.
  • Example 23 The procedure of Example 23 was repeated except that polyoxyethylene nonylphenylether was used as the emulsifier in lieu of the surfactant containing two or more hydroxyl groups per molecule.
  • the emulsifier polyoxyethylene nonylphenylether is a surfactant containing one hydroxyl group per mole­cule, which does not function as a crosslinking agent for the isocyanate compound but rather acts as a crosslinking terminator. Therefore, the degree of cure of the particles was insufficient even after the above reaction time and the particles were sticky and inade­quate in strength. Furthermore, because of this tackiness, the product could not be well dispersed in coating compositions.
  • Example 23 The procedure of Example 23 was repeated except that 300 g of oil-modified alkyd resin in kerosene was used as the protective colloid.
  • the average diameter of the resulting white particles was 47 ⁇ m.
  • the slurry thus obtained was suction-filtered. Owing to the thickening effect of the protective colloid, the filtration procedure required 2 hours. When the filter cake was dried in the air, the residual protective colloid formed a film interconnecting the colored particles to prevent formation of a powdery product. Therefore, the filter cake was washed twice with kerosene and, then, dried in the air to give a powder.
  • Example 23 Compared with Example 23, this Comparative Example required a superfluous washing step for removal of the residual protective colloid.
  • the colored particles recovered by the above washing and drying steps were inferior to the particles of Example 23 in dispersibility for the manufacture of a coating because of the protective colloid that had remained, though in a small amount, and the coating film also betrayed projections formed by aggregation of the particles.
  • This product was a cationic white powder with an average particle diameter of 30 ⁇ m.
  • This product was insoluble in any of methanol, ethanol, hexanol, hexane, isooctane, xylene, toluene, ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl­formamide, ethylcellosolve, ethylcellosolve acetate, machine oil and soybean oil, and thus exhibited excel­lent resistance to chemicals.
  • Example 25 The procedure of Example 25 was repeated except that the amount of the surfactant sucrose trioleate was varied to 200 g or 400 g and the amount of the cross­linking agent hexamethylenediamine was varied to 65 g or 14 g.
  • the average particle diameters of the result­ ing beads are shown in Table 2.
  • Table 2 The amount of sucrose trioleate (g) 200 400 The average particle diameter of the product ( ⁇ m) 25 7.5

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
EP90117311A 1989-09-08 1990-09-07 Procédé de préparation de particules de polymères Expired - Lifetime EP0416659B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP234476/89 1989-09-08
JP234475/89 1989-09-08
JP1234476A JP2613480B2 (ja) 1989-09-08 1989-09-08 高分子粉粒体の製造方法
JP23447589 1989-09-08

Publications (3)

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EP0416659A2 true EP0416659A2 (fr) 1991-03-13
EP0416659A3 EP0416659A3 (en) 1991-08-28
EP0416659B1 EP0416659B1 (fr) 1996-08-21

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EP90117311A Expired - Lifetime EP0416659B1 (fr) 1989-09-08 1990-09-07 Procédé de préparation de particules de polymères

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US (1) US5041467A (fr)
EP (1) EP0416659B1 (fr)
CA (1) CA2024798C (fr)
DE (1) DE69028164T2 (fr)

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EP0509494A2 (fr) * 1991-04-16 1992-10-21 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Procédé pour la préparation de polyuréthane, et des particules vraiment sphériques fines
EP0914364A1 (fr) * 1996-07-22 1999-05-12 Film Specialties, Inc. Composition de revetement anti-buee resistant aux eraflures et integrant des agents tensio-actifs reagissant aux isocyanates
WO2002010243A1 (fr) * 2000-07-27 2002-02-07 3M Innovative Properties Company Dispersion de polyurethanne dans un systeme alcool-eau

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US5165964A (en) * 1991-06-20 1992-11-24 Junkosha Co., Ltd. Process for applying deodorant particles to a membrane
US5462912A (en) * 1991-10-09 1995-10-31 Kao Corporation Agricultural chemical composition enhancer comprising quaternary di(polyoxyalkylene) ammonium alkyl sulfates
ZA981836B (en) * 1997-03-17 1999-09-06 Dow Chemical Co Continuous process for preparing a polyurethane latex.
US6087440A (en) * 1999-02-16 2000-07-11 The Dow Chemical Company Continuous process for preparing a polyurethane latex
KR100458559B1 (ko) * 2000-04-07 2004-12-03 미츠이 다께다 케미칼 가부시키가이샤 수용성 폴리우레탄 및 그 용도
DE10221704A1 (de) * 2001-06-05 2003-01-23 Compo Gmbh & Co Kg Düngemittel mit verzögerter Freisetzung und Verfahren zu dessen Herstellung
US20040209066A1 (en) * 2003-04-17 2004-10-21 Swisher Robert G. Polishing pad with window for planarization
US20060089095A1 (en) 2004-10-27 2006-04-27 Swisher Robert G Polyurethane urea polishing pad
US10308898B2 (en) * 2014-09-26 2019-06-04 The Chemours Company Fc, Llc Method of imparting water repellency with non-fluorinated laundry treatment compositions
KR20220165837A (ko) * 2014-09-26 2022-12-15 더 케무어스 컴퍼니 에프씨, 엘엘씨 비-플루오르화 우레탄계 코팅
JP7110704B2 (ja) * 2018-04-26 2022-08-02 東洋インキＳｃホールディングス株式会社 ポリウレタン樹脂および生体適合性樹脂組成物

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GB1111043A (en) * 1964-04-27 1968-04-24 Wyandotte Chemicals Corp Aqueous polyurethane dispersions
FR1577209A (fr) * 1965-08-24 1969-08-08 Wyandotte Chemicals Corp
EP0317258A2 (fr) * 1987-11-18 1989-05-24 Zeneca Limited Dispersions aqueuses de polyuréethane

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FR1431187A (fr) * 1964-03-02 1966-03-11 Wyandotte Chemicals Corp Procédé de préparation de polymères d'uréthane
GB1111043A (en) * 1964-04-27 1968-04-24 Wyandotte Chemicals Corp Aqueous polyurethane dispersions
FR1577209A (fr) * 1965-08-24 1969-08-08 Wyandotte Chemicals Corp
EP0317258A2 (fr) * 1987-11-18 1989-05-24 Zeneca Limited Dispersions aqueuses de polyuréethane

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509494A2 (fr) * 1991-04-16 1992-10-21 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Procédé pour la préparation de polyuréthane, et des particules vraiment sphériques fines
EP0509494A3 (en) * 1991-04-16 1993-01-13 Dainichiseika Color & Chemicals Mfg. Co. Ltd. Process for the production of polyurethane, and true spherical, fine polyurethane particles
EP0914364A1 (fr) * 1996-07-22 1999-05-12 Film Specialties, Inc. Composition de revetement anti-buee resistant aux eraflures et integrant des agents tensio-actifs reagissant aux isocyanates
EP0914364A4 (fr) * 1996-07-22 1999-09-29 Film Specialties Inc Composition de revetement anti-buee resistant aux eraflures et integrant des agents tensio-actifs reagissant aux isocyanates
WO2002010243A1 (fr) * 2000-07-27 2002-02-07 3M Innovative Properties Company Dispersion de polyurethanne dans un systeme alcool-eau
US6433073B1 (en) 2000-07-27 2002-08-13 3M Innovative Properties Company Polyurethane dispersion in alcohol-water system
AU2001272946B2 (en) * 2000-07-27 2005-09-08 3M Innovative Properties Company Polyurethane dispersion in alcohol-water system
KR100738125B1 (ko) * 2000-07-27 2007-07-10 쓰리엠 이노베이티브 프로퍼티즈 캄파니 알콜-물 계 중의 폴리우레탄 분산액

Also Published As

Publication number Publication date
CA2024798A1 (fr) 1991-03-09
DE69028164D1 (de) 1996-09-26
DE69028164T2 (de) 1997-04-03
EP0416659B1 (fr) 1996-08-21
EP0416659A3 (en) 1991-08-28
US5041467A (en) 1991-08-20
CA2024798C (fr) 1997-07-15

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